On 8 June 1808, at Munich, she married Crown Prince William (1781–1864) becoming Crown Princess of Württemberg. They divorced on 31 August 1814. They had no children.

Her first marriage was arranged to avoid a political marriage arranged by Napoleon. After the marriage ceremony, her spouse said to her: We are victims to politics. They lived separated in the palace and the marriage was never consummated. She spent her time writing letters to her brother Louis, and learning Italian and English. Her first marriage was dissolved by Pope Pius VII to ensure that she be able to marry again according to the Catholic Church.

Both the Emperor and his brother Ferdinand proposed to her, and Ferdinand took back his proposal so that she could accept the Emperor's. The marriage was simple due to the strict economy of the Emperor. The English diplomat Frederick Lamb called the new empress "ugly clever and aimiable, and as the Emperor expresses it: "She can stand a push, the other was nothing but air"."[2] She became popular in Austria and was active in social work; she founded several hospitals and residences for the poor.